CN101218051A - Highly crystalline silver powder and process for production of the same - Google Patents
Highly crystalline silver powder and process for production of the same Download PDFInfo
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- CN101218051A CN101218051A CNA2006800245267A CN200680024526A CN101218051A CN 101218051 A CN101218051 A CN 101218051A CN A2006800245267 A CNA2006800245267 A CN A2006800245267A CN 200680024526 A CN200680024526 A CN 200680024526A CN 101218051 A CN101218051 A CN 101218051A
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- silver powder
- aqueous solution
- acid
- high crystallization
- silver
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 161
- 239000007864 aqueous solution Substances 0.000 claims abstract description 125
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 61
- 238000009826 distribution Methods 0.000 claims abstract description 59
- 229910052709 silver Inorganic materials 0.000 claims abstract description 58
- 239000004332 silver Substances 0.000 claims abstract description 58
- 150000007524 organic acids Chemical class 0.000 claims abstract description 49
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims abstract description 30
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 30
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 29
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 29
- 108010010803 Gelatin Proteins 0.000 claims abstract description 20
- 229920000159 gelatin Polymers 0.000 claims abstract description 20
- 239000008273 gelatin Substances 0.000 claims abstract description 20
- 235000019322 gelatine Nutrition 0.000 claims abstract description 20
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- 239000006228 supernatant Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims description 104
- 230000008025 crystallization Effects 0.000 claims description 104
- 239000003638 chemical reducing agent Substances 0.000 claims description 35
- 239000011164 primary particle Substances 0.000 claims description 35
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 230000001186 cumulative effect Effects 0.000 claims description 14
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229960005137 succinic acid Drugs 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 17
- 238000003756 stirring Methods 0.000 abstract description 15
- 238000005406 washing Methods 0.000 abstract description 9
- 235000010350 erythorbic acid Nutrition 0.000 abstract 1
- 239000004318 erythorbic acid Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 229940026239 isoascorbic acid Drugs 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 63
- 238000006722 reduction reaction Methods 0.000 description 42
- 239000000843 powder Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 18
- 235000015165 citric acid Nutrition 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention aims at providing a process for the production of highly crystalline silver powder which comprises silver particles falling within the fine particle region and has an excellent particle size distribution and highly crystalline silver powder obtained by the process. The aim is attained by a process for the production of highly crystalline silver powder which is characterized by preparing the first aqueous solution containing gelatin, silver nitrate and nitric acid and having a temperature of 45 to 55 C and the second aqueous solution containing erythorbic acid and/or ascorbic acid and a water-soluble organic acid, adding the second aqueous solution mildly to the first aqueous solution, stirring the mixed solution after the completion of the addition to form silver particles through particle growth, allowing the resulting system to stand to settle the silver particles, removing the supernatant, and then subjecting the remainder to filtration and washing to recover the silver particles.
Description
Technical field
The present invention relates to silver powder, the manufacture method of especially high crystallization silver powder and this high crystallization silver powder.
Background technology
In the past, high crystalline (the crystallite particle diameter is big) silver powder, the heat-resisting shrinkage during roasting is good, is processed to silver-colored printing ink or silver paste and is widely used.For example, except that be used to form the roasting purposes under relatively-high temperature such as circuit with ceramic substrate roasting simultaneously, wired circuit, the via (via hole) that also is useful on printed wiring board filled, mixed the purposes that makes its curing with the parts installation with various resinous principles such as adhesives.Particularly the silver powder that uses in silver-colored printing ink that is used to form wirings such as circuit or electrode or silver paste is considered the good silver powder of heat-resisting shrinkage when beginning the requirement roasting from raising as the aspect of the form accuracy of conductor.
The crystallinity that silver powder had, its manufacture method role is very big.For example, in the method for making silver powder, can adopt as disclosed spray-on process in the patent documentation 1 (spy opens the 2003-286502 communique).But the silver powder that adopts this spray-on process to obtain promptly allows to obtain the high silver powder of crystallinity, also is difficult to the silver powder that obtains particulate and have sharp-pointed size distribution.Exactly, by carrying out graded operation repeatedly, should obtain as the silver powder with goods of sharp-pointed size distribution, but consider from the manufacturing cost aspect, be not preferred entirely.Therefore, attempt adopting following wet type autofrettage to obtain silver powder.
For example, disclose a kind of in the patent documentation 2 (special public clear 57-21001 communique), in the mixed aqueous solution of liquor argenti nitratis ophthalmicus and formalin, interpolation is with respect to the aliphatic acid of 0.1～5.0 weight % that separates out the silver amount, stir, thereby toward wherein adding the method that alkaline solution is separated out silver-colored fine powder.Adopt this patent documentation 2 disclosed manufacture methods, can obtain the goods that average grain diameter is 0.8～0.9 μ m as silver-colored fine powder.
In addition, disclose a kind of in the patent documentation 3 (spy opens flat 4-323310 communique), after in the aqueous solvent of containing metal, alloy, slaine etc., dissolving, toward wherein adding alkali, regulate the pH value, again toward wherein adding reducing agent, the method that the lemel end is separated out, it places 10～30 ℃ scope with the liquid temperature, the preparation spheroidal particle.In addition, also disclose a kind ofly, the liquid temperature placed more than 50 ℃ and obtained the method at the lemel end of polyhedral.In the method, the size distribution of resulting metal powder is about 0.3～2.0 μ m.
Adopt the resulting silver powder of disclosed manufacture method in above-mentioned patent documentation 2 and the patent documentation 3,, carry out the heat-resisting shrinkage increasing that sintering adds man-hour owing to its crystallization of separating out is controlled.Therefore, in order to address this problem, a kind of manufacture method of high crystallization silver particles is disclosed in the patent documentation 4 (spy opens the 2000-1706 communique), it is characterized in that, at liquid that acrylic monomers is dissolved in the L-aqueous ascorbic acid with when silver nitrate aqueous solution mixes, make its reaction, irradiation ultraviolet radiation when it reacts.And it is clearly put down in writing, the high crystalline solid silver particles that adopts this manufacture method to obtain, by particle diameter is that monocrystalline and the quasi-crystalline high crystalline solid of 2～4 μ m constitutes, when being that 2 μ m are when following, the problem that shrinkage factor when roasting is arranged is big, when being 4 μ m when above, the concavo-convex big of conductive surface arranged and as problems such as the loss (loss) of circuit increase.Here said high crystallization silver particles is meant that the crystallite size that adopts X-ray diffraction method to calculate from the half-peak breadth at (1.1.1) peak is the particulate more than 400 .
In addition, disclose a kind ofly in the patent documentation 5 (spy opens the 2003-49202 communique), crystallite particle diameter 400～600 , bulk density are 5g/cm
3More than, specific area is 0.15m
2The silver particles that/g is following.And, it is clearly put down in writing, this silver particles adopts following manufacture method to obtain, this manufacture method is characterised in that, make the alkaline aqueous solution that contains silver ion (ammonium hydroxide aqueous solution+be selected from more than a kind of NaOH and potassium hydroxide) and aqueous hydrogen peroxide solution (as required, adding the material that is selected from the group of forming by aliphatic acid, soap and these derivative more than a kind) reaction.And it is clearly put down in writing, and is 400～600 in the scope of the crystallite particle diameter of this resulting silver particles, and when being lower than 400 , as high-temperature roasting conductor paste silver granuel, its crystallinity is low, when greater than 600 , and silver particles shape instability.In addition, though the bulk density that silver granuel arranged in patent documentation 5 at 5g/cm
3More than, the specific area of silver granuel is at 0.15m
2The description that/g is following, but because this two key element all is to be prerequisite with the pass with original particle diameter, and owing to do not have explanation to particle diameter fully, thereby the key element that the document limits powder is inadequate.
Patent documentation 1: the spy opens the 2003-286502 communique
Patent documentation 2: special public clear 57-21001 communique
Patent documentation 3: the spy opens flat 4-323310 communique
Patent documentation 4: the spy opens the 2000-1706 communique
Patent documentation 5: the spy opens the 2003-49202 communique
Summary of the invention
The problem that invention will solve
Relate to the reducing agent L-ascorbic acid that adopts in the disclosed manufacture method in the above-mentioned patent documentation 4 of highly crystalline silver powder, it costs an arm and a leg, thereby becomes the major reason that causes the goods price to rise.In addition, the reducing agent main body adopts ascorbic acid and the resulting high crystallization silver particles of irradiation ultraviolet radiation when reduction reaction, there are roughly proportional relation in its particle diameter and crystallite particle size values, when obtaining particle diameter and be the big particle diameter powder of 2 μ m～4 μ m, can obtain the goods of certain stabilised quality.Yet, can confirm, even obtain particle diameter less than 2 μ m and crystallite particle diameter particulate silver powder greater than 400 , because the deviation of the crystallite particle diameter of this manufacture method is big, the process stability shortcoming, shrinkage factor during less than the roasting of the particulate silver powder of 2 μ m strengthens, and the particulate under a lot of situations can not get good heat-resisting shrinkage.
In addition, the solution that adopts in the disclosed manufacture method in the patent documentation 5, owing to adopt the big medicines of stink such as ammonia spirit and ammonium nitrate, existing causes operating environment deterioration, the shortcoming of the copper components damage in the acceleration equipment.And owing to adopt the fierce aqueous hydrogen peroxide solution of chemical valence change, so the quality stability of solution shortcoming, the average grain diameter deviation of resulting silver powder is big, the control difficulty of particle diameter, size distribution.
From as can be known above-mentioned, though can obtain the silver powder of particulate and high crystalline, the high crystallization silver powder that fully satisfies market demands does not still exist.
Solve the method for problem
For address the above problem concentrate one's attention on research found that the silver powder that adopts following manufacture method to obtain has in the past unexistent high crystalline of silver powder and micronize level.
The manufacture method of high crystallization silver powder: the manufacture method of high crystallization silver powder of the present invention, it is characterized in that, preparation is with gelatin, silver nitrate and nitric acid the 1st aqueous solution soluble in water, and the 2nd aqueous solution that has dissolved arabo-ascorbic acid and water-soluble organic acid, then, in the 1st aqueous solution, slowly add the 2nd aqueous solution, stir after adding termination, make the particle growth and generate silver particles, leave standstill then, make the silver particles sedimentation, then, discarded supernatant filters, washs, and obtains high crystallization silver powder.
In the manufacture method of high crystallization silver powder of the present invention, the gelatin concentration in preferred above-mentioned the 1st aqueous solution is 2g/L～10g/L.
In the manufacture method of high crystallization silver powder of the present invention, the silver nitrate concentration in preferred above-mentioned the 1st aqueous solution is to be 50g/L～150g/L with the silver metering.
In the manufacture method of high crystallization silver powder of the present invention, the free concentration of nitric acid that adds in preferred above-mentioned the 1st aqueous solution is to adjust aqueous solution of nitric acid and be 40g/L～120g/L.
In the manufacture method of high crystallization silver powder of the present invention, the arabo-ascorbic acid concentration in preferred above-mentioned the 2nd aqueous solution is 45g/L～120g/L.
In the manufacture method of high crystallization silver powder of the present invention, the water-soluble organic acid concentration in preferred above-mentioned the 2nd aqueous solution is 1g/L～50g/L.
In the manufacture method of high crystallization silver powder of the present invention, preferred above-mentioned water-soluble organic acid is any or composition more than 2 kinds of DL-malic acid, citric acid, formic acid, valeric acid, isovaleric acid, butanedioic acid, propionic acid, lactic acid, adipic acid.
High crystallization silver powder: high crystallization silver powder of the present invention is that the argentiferous ion solution is added arabo-ascorbic acid and/or ascorbic acid and water-soluble organic acid as reducing agent, and its reduction is separated out and the silver powder that obtains.
And above-mentioned highly crystalline silver powder is characterized in that, primary particle size is that 0.07 μ m～4.5 μ m, crystallite particle diameter are more than 200 .
In addition, preferred above-mentioned highly crystalline silver powder shows following powder characteristics, that is, when adopting laser diffraction and scattering formula particle size distribution method to measure, volume cumulative mean particle diameter D
50Be 0.1 μ m～5.0 μ m, size distribution index (D
90-D
10)/D
50Value be below 1.5.
In addition, high crystallization silver powder of the present invention contains big particle with certain proportion usually, but when adopting laser diffraction and scattering formula particle size distribution method to measure, volume accumulation maximum particle diameter D
MaxBe below the 16.0 μ m.
In addition, the specific area of preferred high crystallization silver powder of the present invention is 0.2m
2More than/the g.
The effect of invention
The manufacture method of high crystallization silver powder of the present invention with reducing agent and water-soluble organic acid, can be suitable for the high crystallization silver powder from the big particle diameter of particulate manufacturing by also.Particularly, the influence of operations such as the variations in temperature when being difficult to be subjected to reduction reaction, change in concentration change can be made high crystallization silver powder with high yield.
The high crystallization silver powder that adopts the manufacture method of high crystallization silver powder of the present invention to obtain has following powder characteristics, that is, and and the volume cumulative mean particle diameter D that adopts laser diffraction and scattering formula particle size distribution method to measure
50Be that 0.1 μ m～5.0 μ m, crystallite particle diameter are that 200 are above, size distribution index (D
90-D
10)/D
50Value be below 1.5.As can be known clear and definite from this powder characteristics institute, it has in the particle size range (2 μ m～5 μ m) that in the past exists the sharp-pointed size distribution of unexistent level in the past.And, even particle diameter, still has stable big crystallite particle diameter less than the goods of 2 μ m and has sharp-pointed size distribution.Therefore, adopt the high crystallization silver powder that the present invention relates to make silver paste, with the electrically conductive film that this silver paste forms, heat-resisting shrinkage is good and surface roughness electrically conductive film is smooth.
The specific embodiment
Below, the specific embodiment that is used to implement high crystallization silver powder of the present invention and manufacture method thereof is described.
The manufacture method of high crystallization silver powder: the manufacture method of high crystallization silver powder of the present invention, it is characterized in that, preparation is with gelatin, silver nitrate and nitric acid the 1st aqueous solution soluble in water, and the 2nd aqueous solution that has dissolved arabo-ascorbic acid and/or ascorbic acid and water-soluble organic acid, then, slowly add the 2nd aqueous solution toward the 1st aqueous solution, stir after adding termination, make the particle growth and generate silver particles, leave standstill then, make the silver particles sedimentation, then, discarded supernatant filters, washs, and obtains high crystallization silver powder.
At first, the 1st aqueous solution is described.The 1st aqueous solution is the solution that contains silver salt, is the solution that makes gelatin, silver nitrate and nitric acid water-soluble.Gelatin described here, conduct also contain than the notion of the glue of the purity difference of gelatin to be recorded and narrated.This gelatin is the material of the reduction rate (reaction speed) when being used to control reduction and separating out high crystallization silver powder.In addition, gelatin has the function of the steric hindrance agent of the particle coacervation of separating out as the inhibition reduction, the cohesion between the particle that the inhibition reduction is separated out, and the size distribution of resulting high crystallization silver powder becomes sharply, is preferred.And preferably the gelatin concentration in above-mentioned the 1st aqueous solution is 2g/L～10g/L.When this gelatin concentration was lower than 2g/L, the reduction rate when the 1st aqueous solution and the 2nd reactant aqueous solution accelerated, and the crystallite particle diameter of the silver particles of not only separating out strengthens, and the cohesion between the particle also becomes significantly the silver powder that can not get having sharp-pointed size distribution.On the other hand, when this gelatin concentration during greater than 10g/L, reduction reaction speed is slack-off, not only can't satisfy industrial production, and the deviation of crystallite particle diameter also strengthens.
Silver nitrate concentration in preferred above-mentioned the 1st aqueous solution is to be 50g/L～150g/L with the silver metering.When being lower than 50g/L, the silver amount that reduction is separated out is few when silver nitrate concentration (with the silver metering), and because the particle diameter of the silver of separating out is too small, the crystallite particle diameter also diminishes.On the other hand, when silver nitrate concentration (with silver metering) during greater than 150g/L, from considering with the balance of reducing agent etc., residual have a unreduced silver ion, cause the waste of resource, simultaneously, because the site of reduction reaction is too much, the cohesion of precipitation particles is remarkable, the dispersed good volume cumulative mean particle diameter D of particle
50The yield that is the above high crystallization silver powder of 0.1 μ m reduces.
In addition, the free concentration of nitric acid in preferred above-mentioned the 1st aqueous solution is that the interpolation aqueous solution of nitric acid is adjusted to 40g/L～120g/L.Should free concentration of nitric acid, be for the silver ion mudization in the 1st aqueous solution that prevents to contain silver salt, separate out silver particles with the reducing agent reduction and the factor that need manage effectively.
The liquid temperature of preferred the 1st aqueous solution is 45 ℃～55 ℃.When this liquid temperature was lower than 45 ℃, gelatin, silver nitrate were difficult to rapid the mixing with nitric acid, and the speed of the reduction reaction that interpolation the 2nd aqueous solution described later carries out is slack-off, is difficult to make the highly crystalline silver powder with suitable size distribution.When the liquid temperature was higher than 55 ℃, the decomposition of gelatin was promoted, the solution lifetime, and can not get having the silver powder of suitable crystallite particle diameter.
Next, the 2nd aqueous solution is described.The 2nd aqueous solution is the aqueous solution that contains reducing agent.And, as the arabo-ascorbic acid and/or the ascorbic acid of reducing agent, both be meant and can use arabo-ascorbic acid, ascorbic acid separately respectively as reducing agent, also can and use arabo-ascorbic acid and ascorbic acid as reducing agent.Therefore, the concentration of following arabo-ascorbic acid and/or ascorbic acid, be to comprise and with the notion of the situation of arabo-ascorbic acid and ascorbic acid, and the weight ratio of the arabo-ascorbic acid of usefulness and ascorbic acid is, [arabo-ascorbic acid]: [ascorbic acid]=0.1: 9.9～9.9: 0.1, if consider more stable process stability, then preferred [arabo-ascorbic acid]: [ascorbic acid]=0.5: 9.9～9.9: 0.5, if consider especially stable process stability, then preferred [arabo-ascorbic acid]: [ascorbic acid]=1: 9～9: 1.
The arabo-ascorbic acid in preferred above-mentioned the 2nd aqueous solution and/or the concentration of ascorbic acid are 45g/L～120g/L.This reductant concentration, by with the relation decision of the silver content of the 1st aqueous solution, but the reductant concentration in the silver concentration in the 1st aqueous solution and the 2nd aqueous solution is when being in suitable scope, reducible particulate silver powder of separating out below the particle diameter 2 μ m.That is, when the concentration of arabo-ascorbic acid in the 2nd aqueous solution and/or ascorbic acid was lower than 45g/L, the silver ion reduction in the 1st aqueous solution was insufficient, cause the wasting of resources, simultaneously, the size distribution of resulting silver powder is smooth, can not get having the high crystallization silver powder of good crystallite particle diameter.On the other hand, when the arabo-ascorbic acid in the 2nd aqueous solution and/or the concentration of ascorbic acid surpass 120g/L, surpass the amount of the necessary reducing agent of silver ion reduction in the 1st aqueous solution, caused the waste of reducing agent, make reduction reaction too fast simultaneously, the particle diameter of crystallite diminishes.
In above-mentioned the 2nd aqueous solution, add above-mentioned reducing agent, interpolation water-soluble organic acid this point, have big feature.This water-soluble organic acid shows that the crystallite particle diameter of the silver-colored crystallization that the reduction of sening as an envoy to is separated out becomes big effect, even particle diameter less than the particulate silver powder of 2 μ m, it is big that this crystallite particle diameter also may become.And this water-soluble organic acid also plays making the size distribution of the reduction silver powder of separating out good, generates the function of the silver powder of the dispersed good sharp-pointed size distribution of particle.The so-called water-soluble organic acid here is meant any or composition more than 2 kinds of DL-malic acid, citric acid, formic acid, valeric acid, isovaleric acid, butanedioic acid, propionic acid, lactic acid, adipic acid.
In addition, preferably this water-soluble organic acid concentration is 1g/L～50g/L.When the water-soluble organic acid concentration in the 2nd aqueous solution was lower than 1g/L, the effect that can not get making the crystallite particle diameter of the crystallization of the silver that reduction separates out to increase had lost the meaning of using water-soluble organic acid.On the other hand, when water-soluble organic acid concentration surpassed 50g/L, the effect that this crystallite particle diameter strengthens can not be brought up to its above effect, and on the contrary, the size distribution of resulting silver powder has the tendency of variation.
Spend 10 minutes～time of 60 minutes slowly adds the 2nd aqueous solution in the 1st above-mentioned aqueous solution.When only mixed once was promptly whole the 1st aqueous solution and the 2nd aqueous solution, the size distribution of resulting silver powder became smooth, can not get the goods of sharp-pointed size distribution, and the generation of coarse grain is remarkable.Therefore, when incorporation time was less than 10 minutes, with only mixed once is same, the size distribution of the silver powder that obtains was smooth, the increasing of coarse grain.On the other hand,, productivity is reduced,, can not expect the improvement of size distribution even add more lentamente even incorporation time surpasses 60 minutes.
This moment is with respect to the addition of the 2nd aqueous solution of the 1st aqueous solution, with the silver amount that contains in the 1st aqueous solution as benchmark, as long as supply with the reduction dosage of the minimum flow that coincide with the essential reaction equivalent of this reduction.Consider as benchmark with the silver amount that contains in the 1st aqueous solution this moment, reduce the reduction dosage of surplus of reduction dosage of necessary reaction equivalent also without any problem even add to surpass this.Temperature during to reduction reaction is not particularly limited, but for big change takes place the liquid temperature that does not make the 1st aqueous solution, preferably adopts the scope of room temperature～50 ℃.When employing surpassed 50 ℃ temperature, the evaporation of moisture was remarkable, easily causes component fluctuation in the incorporation time of the 1st aqueous solution and the 2nd aqueous solution.
In addition, after adding the 2nd aqueous solution in the 1st aqueous solution and stopping, stirred 3～5 minutes, carry out the particle growth, the generation silver particles.When mixing time was less than 3 minutes, reduction reaction can not fully be finished sometimes, thereby, be not preferred.On the other hand, even mixing time surpasses 5 minutes, reduction reaction stops already fully, does not have Practical significance.
In addition, after adding the 2nd aqueous solution in the 1st aqueous solution and stopping, if the reduction of silver does not take place separates out, Compositional balance in the 1st aqueous solution that then should the stage and the reduction reaction liquid of the 2nd aqueous solution is: gelatin concentration 2g/L～10g/L, silver nitrate concentration (with the silver metering) 50g/L～150g/L, free concentration of nitric acid 40g/L～120g/L is as the arabo-ascorbic acid and/or the ascorbic acid 45g/L～120g/L of reducing agent, water-soluble organic acid concentration 1g/L～50g/L.
After above-mentioned restoring operation stops, leave standstill, make the silver particles sedimentation.Then, discarded supernatant filters, washs, and can obtain high crystallization silver powder.
High crystallization silver powder: high crystallization silver powder of the present invention is that the argentiferous ion solution is added the silver powder that as the arabo-ascorbic acid of reducing agent and/or ascorbic acid and water-soluble organic acid its reduction is separated out and obtain.
Above-mentioned high crystallization silver powder is characterized in that, primary particle size is that 0.07 μ m～4.5 μ m, crystallite particle diameter are more than 200 .High crystallization silver powder of the present invention adds water-soluble organic acid as reducing agent in the argentiferous ion solution and obtains with arabo-ascorbic acid and/or ascorbic acid.By and use this water-soluble organic acid, it is big to obtain the crystallite particle diameter, and also has the high crystallization silver powder of good crystallite particle diameter and sharp-pointed size distribution in the particulate scope of primary particle size less than 2.0 μ m.Can reach the particle diameter of wide region and the crystallite particle diameter that primary particle size is in 0.07 μ m～4.5 μ m here, is the above high crystallines of 200 .In addition, so-called primary particle size is meant with scanning electron microscope and observes the highly crystalline silver powder particle, directly observes the particle diameter of 100 contained in this visual field particles, the value of obtaining as its mean value.In this primary particle size scope, the particle diameter that can be described as particulate is meant 0.07 μ m～less than 2.0 μ m, preferred 0.07 μ m～1.5 μ m, more preferably 0.07 μ m～1.0 μ m.Generally speaking, particle diameter and crystallite particle diameter have individual proportionality coefficient, when primary particle size surpasses 0.3 μ m, can obtain surpassing the crystallite particle diameter of 400 .The situation of high crystallization silver powder of the present invention even particle diameter is the scope of 0.07 μ m～0.3 μ m, also can be stablized the crystallite particle diameter that obtains 200 ～300 magnitudes.As above-mentioned particle diameter be in superfine scope, the crystallite particle diameter is the silver powder more than 200 , do not exist in the past.In addition, the mensuration of crystallite particle diameter of the present invention is the RINT2000X ray diffraction device that adopts Rigaku Denki Co., Ltd to make, and measures with Weir inferior (Wilson) method (X-ray diffraction crystallite particle diameter determination method).
In addition, when adopting laser diffraction and scattering formula particle size distribution method to measure highly crystalline silver powder, demonstrate the powder characteristics of the following stated with above-mentioned powder characteristics, that is, and volume cumulative mean particle diameter D
50Be 0.1 μ m～5.0 μ m, size distribution index (D
90-D
10)/D
50Value be below 1.5.
That is be the volume cumulative mean particle diameter D that the corresponding laser diffraction and scattering formula particle size distribution method of the scope of 0.07 μ m～4.5 μ m is measured, with primary particle size
50Value for about 0.1 μ m～5.0 mu m ranges.The primary particle size that the primary particle size scope is classified as particulate is 0.07 μ m～less than the volume cumulative mean particle diameter D of 2.0 μ m goods
50Almost complete scope at 0.1 μ m～1.6 μ m.Primary particle size is the volume cumulative mean particle diameter D of the goods of 0.07 μ m～1.5 μ m
50Almost complete scope at 0.1 μ m～1.2 μ m.Primary particle size is the volume cumulative mean particle diameter D of the goods of 0.07 μ m～1.0 μ m
50Almost complete scope at 0.1 μ m～0.7 μ m.
In addition, high crystallization silver powder of the present invention has the (D as the dispersed index of expression particle
90-D
10)/D
50Value be dispersiveness below 1.5.Here, so-called (D
90-D
10)/D
50Value, be meant the D of volume accumulation particle diameter 90%
90D with volume accumulation particle diameter 10%
10Poor, with volume cumulative mean particle diameter D
50The value of removing and obtaining.That is, with volume cumulative mean particle diameter D
50As benchmark, the width of calculating size distribution reaches volume cumulative mean particle diameter D actually
50Several times, this value is more near 1, the distribution curve of expression size distribution is more sharp-pointed.Therefore, should (D
90-D
10)/D
50Value below 1.5, be meant that size distribution is quite sharp-pointed, particle diameter that we can say nearly all particle is volume cumulative mean particle diameter D
50Below 1.5 times.Relative therewith, though in the past adopt reducing agent such as ascorbic acid separately the time, if only observe the crystallite particle diameter, then also can obtain having the silver powder of the crystallite particle diameter that surpasses 400 .Yet, in this case, when primary particle size less than 1.6 μ m (volume cumulative mean particle diameter D
50Be about 2.0 μ m) time, the size distribution of resulting silver powder is smooth, forms to have (D
90-D
10)/D
50Value surpass the silver powder of 2.0 smooth size distribution.With this silver powder system cream with smooth size distribution, when forming conducting film, its conducting film rough surface, thereby not preferred.
Employing arabo-ascorbic acid and/or ascorbic acid are made reducing agent and are also used with water-soluble organic acid, from the high crystallization silver powder that the argentiferous ion solution obtains, contain corase particles usually in certain proportion, but be prerequisite to have above-mentioned powder characteristics, thereby, volume accumulation maximum particle diameter D
MaxBelow 16.0 μ m.This maximum particle diameter is seen in a sense, can be used as coarse grain understanding, according to occasion, can remove from goods by progressive operation.
In addition, adopting the specific area of the of the present invention high crystallization silver powder that above-mentioned manufacture method obtains is 0.2m
2The scope that/g is above.Learn that from inventor's etc. result of study it is 0.2m
2/ g～3.5m
2The scope of/g.More form the particle with smooth surface, this specific area value is littler, and the viscosity when livering or printing ink is lower.
Embodiment 1
The preparation of the 1st aqueous solution: in pure water 250g, add gelatin 1.0g, silver nitrate 50g, nitric acid 26.4g, while stirring the liquid temperature is heated to 50 ℃, make dissolving and make.
The preparation of the 2nd aqueous solution: as the arabo-ascorbic acid 26.4g of reducing agent, as the DL-malic acid 4.2g of water-soluble organic acid, be dissolved in pure water 250g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.Add mixing of the 1st aqueous solution and the 2nd aqueous solution stop after, stirred 5 minutes, make and separate out silver particles and grow.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing according to usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 1 with other embodiment and comparative example.
Embodiment 2
The preparation of the 1st aqueous solution: similarly to Example 1, omit its record for avoiding repeating record.
The preparation of the 2nd aqueous solution: as the arabo-ascorbic acid 26.4g of reducing agent, as the citric acid 3.6g of water-soluble organic acid, be dissolved in pure water 250g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing by usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 1 with other embodiment and comparative example.
Embodiment 3
The preparation of the 1st aqueous solution: in pure water 550g, add gelatin 3.3g, silver nitrate 55g, nitric acid 27g, while stirring the liquid temperature is heated to 50 ℃, make dissolving and make.
The preparation of the 2nd aqueous solution: as the arabo-ascorbic acid 28.1g of reducing agent, as the DL-malic acid 4.47g of water-soluble organic acid, be dissolved in pure water 250g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing by usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 2 with other embodiment and comparative example.
Embodiment 4
The preparation of the 1st aqueous solution: similarly to Example 3, omit its record for avoiding repeating record.
The preparation of the 2nd aqueous solution: as the arabo-ascorbic acid 28.1g of reducing agent, as the citric acid 3.83g of water-soluble organic acid, be dissolved in pure water 550g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing according to usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 2 with other embodiment and comparative example.
Embodiment 5
The preparation of the 1st aqueous solution: in pure water 700g, add gelatin 4.0g, silver nitrate 66g, nitric acid 32.4g, while stirring the liquid temperature is heated to 50 ℃, make dissolving and make.
The preparation of the 2nd aqueous solution: as the ascorbic acid 33.8g of reducing agent, as the citric acid 4.6g of water-soluble organic acid, be dissolved in pure water 700g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing according to usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 3 with other embodiment and comparative example.
Embodiment 6
The preparation of the 1st aqueous solution: similarly to Example 5, omit its record for avoiding repeating record.
The preparation of the 2nd aqueous solution: as the ascorbic acid 33.8g of reducing agent, as the DL-malic acid 6.0g of water-soluble organic acid, be dissolved in pure water 700g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.And, after the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing by usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 3 with other embodiment and comparative example.
Embodiment 7
The preparation of the 1st aqueous solution: similarly to Example 5, omit its record for avoiding repeating record.
The preparation of the 2nd aqueous solution: as the ascorbic acid 16.9g of reducing agent and arabo-ascorbic acid 16.9g, as the DL-malic acid 6.0g of water-soluble organic acid, be dissolved in pure water 720g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing by usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 4 with other embodiment and comparative example.
Embodiment 8
The preparation of the 1st aqueous solution: similarly to Example 5, omit its record for avoiding repeating record.
The preparation of the 2nd aqueous solution: as the ascorbic acid 16.9g of reducing agent and arabo-ascorbic acid 16.9g, as the citric acid 4.6g of water-soluble organic acid, be dissolved in pure water 720g, be mixed with solution.
The reduction of high crystallization silver powder is separated out: in above-mentioned the 1st aqueous solution of 50 ℃ of liquid temperature, spend 30 minutes and slowly add the 2nd aqueous solution.After the 1st aqueous solution and the 2nd aqueous solution interpolation termination, stirred 5 minutes, make and separate out the silver particles growth.
The filtration of high crystallization silver powder is taked: after stirring in 5 minutes stopped, former state left standstill, and made the silver powder precipitation of generation, and discarded its supernatant carries out filtration washing by usual way, obtains high crystallization silver powder.The powder characteristics of this high crystallization silver powder is shown in Table 4 with other embodiment and comparative example.
Comparative example
Comparative example 1
In this comparative example, except that the water-soluble organic acid (DL-malic acid) of the 2nd aqueous solution that omits embodiment 1, other conditions produce silver powder similarly to Example 1.The powder characteristics of this silver powder is shown in Table 1 with other embodiment and comparative example.
Comparative example 2
In this comparative example, except that the water-soluble organic acid (DL-malic acid) of the 2nd aqueous solution that omits embodiment 3, other conditions produce silver powder similarly to Example 1.The powder characteristics of this silver powder is shown in Table 2 with other embodiment and comparative example.
Comparative example 3
In this comparative example, except that the water-soluble organic acid (citric acid) of the 2nd aqueous solution that omits embodiment 5, other conditions produce silver powder similarly to Example 1.The powder characteristics of this silver powder is shown in Table 3 with other embodiment and comparative example.
Comparative example 4
In this comparative example, except that the water-soluble organic acid (DL-malic acid) of the 2nd aqueous solution that omits embodiment 7, other conditions produce silver powder similarly to Example 1.The powder characteristics of this silver powder is shown in Table 4 with other embodiment and comparative example.
The contrast of embodiment and comparative example
The contrast of embodiment 1, embodiment 2 and comparative example 1: embodiment 1 is different DL-malic acid and citric acids with the water-soluble organic acid with reducing agent and usefulness among the embodiment 2, then do not use the water-soluble organic acid of embodiment 1 in the comparative example 1, they are shown in Table 1 simultaneously to contrast.
Table 1
| Sample | Primary particle size | D 10 | D 50 | D 90 | D max | SSA | The crystallite particle diameter | (D 90-D 10)/D 50 |
| μm | m 2/g | | ||||||
| Embodiment 1 | 3.96 | 2.83 | 4.05 | 6.98 | 13.1 | 0.29 | 525 | 1.02 |
| Embodiment 2 | 3.86 | 2.54 | 4.12 | 7.02 | 15.6 | 0.28 | 522 | 1.08 |
| Comparative example 1 | 3.33 | 2.38 | 4.02 | 8.46 | 18.5 | 0.26 | 546 | 1.51 |
In this table 1, the D that shows primary particle size, adopts laser diffraction and scattering formula particle size distribution method to measure
10, D
50, D
90, D
Max, specific area (SSA), crystallite particle diameter and (D
90-D
10)/D
50Value.At first, observe primary particle size, as can be known, compare, do not use the comparative example 1 of water-soluble organic acid to obtain the slightly little silver powder of primary particle size with embodiment 1 and embodiment 2.Here, with the D of embodiment 1, embodiment 2 and comparative example 1
10, D
50, D
90, D
Max, each value of specific area (SSA), crystallite particle diameter compares, not talkative its value has very big-difference.Relative therewith, when observing (D
90-D
10)/D
50Value the time, compare with comparative example 1, the value of embodiment 1 and embodiment 2 obviously diminishes.That is, compare with the size distribution of comparative example 1, the size distribution of embodiment 1 and embodiment 2 is sharp-pointed size distribution, its particle size unanimity.
Inquire into this and find that the silver powder that obtains in the comparative example 1 is compared with embodiment 1 and embodiment 2 as a result the time, its primary particle size has the tendency that diminishes, but the cohesion of the silver particles that its reduction is separated out is remarkable, is difficult to actual use.Relative therewith, as to adopt the manufacture method of embodiment 1 and embodiment 2 to obtain high crystallization silver powder because difficulty causes cohesion, can form have coarse grain generation less, the goods of the dispersed good balance of particle.
The contrast of embodiment 3, embodiment 4 and comparative example 2: embodiment 3 is different DL-malic acid and citric acids with the water-soluble organic acid with reducing agent and usefulness among the embodiment 4, then do not use the water-soluble organic acid of embodiment 3 in the comparative example 2, they are shown in Table 2 simultaneously, to contrast.
Table 2
| Sample | Primary particle size | D 10 | D 50 | D 90 | D max | SSA | The crystallite particle diameter | (D 90-D 10)/D 50 |
| μm | m 2/g | | ||||||
| Embodiment 3 | 0.89 | 0.62 | 1.02 | 1.88 | 3.6 | 0.85 | 438 | 1.24 |
| Embodiment 4 | 0.94 | 0.69 | 1.08 | 1.98 | 3.9 | 0.83 | 432 | 1.19 |
| Comparative example 2 | 0.74 | 0.45 | 1.16 | 2.84 | 5.5 | 0.86 | 438 | 2.06 |
In this table 2, the D that shows primary particle size, adopts laser diffraction and scattering formula particle size distribution method to measure
10, D
50, D
90, D
Max, specific area (SSA), crystallite particle diameter and (D
90-D
10)/D
50Value.At first, observe primary particle size, as can be known, compare, do not use the comparative example 2 of water-soluble organic acid, obtain the little silver powder of primary particle size with embodiment 3 and embodiment 4.Here, to the D of embodiment 3, embodiment 4 and comparative example 2
10, D
50, D
90, D
Max, each value of specific area (SSA), crystallite particle diameter compares.At first, observe primary particle size and D
10, then embodiment 3 and embodiment 4 are big than comparative example 2 as can be known.When observing D
50The time, then embodiment 3 and embodiment 4 and comparative example 2 no big differences.When observing D
90And D
MaxThe time, then comparative example 2 is big than embodiment 3 and embodiment 4.In this stage, can envision with the size distribution of comparative example 2 and compare, the size distribution of embodiment 3 and embodiment 4 can reach good acuteness.Secondly, the value of specific area (SSA) and crystallite particle diameter, then not talkative have big difference.When observing (D
90-D
10)/D
50Value the time, compare with comparative example 2, the value of embodiment 3 and embodiment 4 diminishes significantly.That is, compare with the size distribution of comparative example 2, the size distribution of embodiment 3 and embodiment 4 is sharp-pointed size distribution, its particle size unanimity.
Inquire into this and find that the silver powder that obtains in the comparative example 2 is compared with embodiment 3 and embodiment 4 as a result the time, its primary particle size has the tendency that diminishes, but the cohesion of the silver particles that its reduction is separated out is remarkable, is difficult to actual use.Relative therewith, as to adopt the manufacture method of embodiment 3 and embodiment 4 to obtain high crystallization silver powder because difficulty causes cohesion, can form have coarse grain generation less, the goods of the dispersed good balance of particle.
The contrast of embodiment 5, embodiment 6 and comparative example 3: embodiment 5 is different DL-malic acid and citric acids with the water-soluble organic acid with reducing agent and usefulness among the embodiment 6, then do not use the water-soluble organic acid of embodiment 5 in the comparative example 3, they are shown in Table 3 simultaneously, to contrast.
Table 3
| Sample | Primary particle size | D 10 | D 50 | D 90 | D max | SSA | The crystallite particle diameter | (D 90-D 10)/D 50 |
| μm | m 2/g | | ||||||
| Embodiment 5 | 0.85 | 0.65 | 0.98 | 1.82 | 3.5 | 0.90 | 408 | 1.19 |
| Embodiment 6 | 0.84 | 0.62 | 0.96 | 1.74 | 3.5 | 0.89 | 405 | 1.16 |
| Comparative example 3 | 0.68 | 0.50 | 1.10 | 2.94 | 5.5 | 0.95 | 407 | 2.22 |
In this table 3, the D that shows primary particle size, adopts laser diffraction and scattering formula particle size distribution method to measure
10, D
50, D
90, D
Max, specific area (SSA), crystallite particle diameter and (D
90-D
10)/D
50Value.At first, observe primary particle size, as can be known, compare, do not use the comparative example 3 of water-soluble organic acid, obtain the little silver powder of primary particle size with embodiment 5 and embodiment 6.Here, to the D of embodiment 5, embodiment 6 and comparative example 3
10, D
50, D
90, D
Max, each value of specific area (SSA), crystallite particle diameter compares.When observing D
10The time, embodiment 5 and embodiment 6 are big than comparative example 3.When observing D
50The time, embodiment 5 and embodiment 6 compare with comparative example 3 does not have big difference.When observing D
90And D
MaxThe time, comparative example 3 is big than embodiment 5 and embodiment 6.In this stage, can envision with the size distribution of comparative example 3 and compare, the size distribution of embodiment 5 and embodiment 6 can reach good acuteness.Secondly, the value of specific area (SSA) and crystallite particle diameter, not talkative have big difference.When observing (D
90-D
10)/D
50Value the time, compare with comparative example 3, the value of embodiment 5 and embodiment 6 diminishes significantly.That is, compare with the size distribution of comparative example 3, the size distribution of embodiment 5 and embodiment 6 is sharp-pointed size distribution, its particle size unanimity.
Inquire into it and find that the silver powder that obtains in the comparative example 3 is compared with embodiment 5 and embodiment 6 as a result the time, its primary particle size has the tendency that diminishes, but the cohesion of the silver particles that its reduction is separated out is remarkable, is difficult to actual use.Relative therewith, as to adopt the manufacture method of embodiment 5 and embodiment 6 to obtain high crystallization silver powder because difficulty causes cohesion, can form have coarse grain generation less, the goods of the dispersed good balance of particle.
The contrast of embodiment 7, embodiment 8 and comparative example 4: embodiment 7 is different DL-malic acid and citric acids with the water-soluble organic acid with reducing agent and usefulness among the embodiment 8, do not use the water-soluble organic acid of embodiment 7 in the comparative example 4, they are shown in Table 4 simultaneously, to contrast.
Table 4
| Sample | Primary particle size | D 10 | D 50 | D 90 | D max | SSA | The crystallite particle diameter | (D 90-D 10)/D 50 |
| μm | m 2/g | | ||||||
| Embodiment 7 | 0.82 | 0.58 | 0.94 | 1.68 | 2.3 | 0.99 | 401 | 1.17 |
| Embodiment 8 | 0.86 | 0.59 | 0.92 | 1.58 | 2.1 | 1.01 | 400 | 1.08 |
| Comparative example 4 | 0.65 | 0.53 | 1.09 | 3.33 | 5.5 | 0.99 | 403 | 2.57 |
In this table 4, the D that shows primary particle size, adopts laser diffraction and scattering formula particle size distribution method to measure
10, D
50, D
90, D
Max, specific area (SSA), crystallite particle diameter and (D
90-D
10)/D
50Value.At first, observe primary particle size, as can be known, compare, do not use the comparative example 4 of water-soluble organic acid to obtain the little silver powder of primary particle size with embodiment 7 and embodiment 8.Here, to the D of embodiment 7, embodiment 8 and comparative example 4
10, D
50, D
90, D
Max, each value of specific area (SSA), crystallite particle diameter compares.Thus, about D
90And D
MaxValue, can think that compare with embodiment 7 and embodiment 8, the value of comparative example 4 is big significantly, the ratio that forms coarse grain is many.Other value, then not talkative have big difference.When observing (D
90-D
10)/D
50Value the time, compare with comparative example 4, the value of embodiment 7 and embodiment 8 diminishes significantly.That is, compare with the size distribution of comparative example 4, the size distribution of embodiment 7 and embodiment 8 is sharp-pointed size distribution, its particle size unanimity.
Inquire into it and find that the silver powder that obtains in the comparative example 4 is compared with embodiment 7 and embodiment 8 as a result the time, its primary particle size has the tendency that diminishes, but the cohesion of the silver particles that its reduction is separated out is remarkable, is difficult to actual use.Relative therewith, as to adopt the manufacture method of embodiment 7 and embodiment 8 to obtain high crystallization silver powder because difficulty causes cohesion, can form have coarse grain generation less, the goods of the dispersed good balance of particle.
Industrial applicibility
Compare with high crystallization silver powder in the past, above-mentioned high crystallization silver powder is the goods high crystallization and that have sharp-pointed size distribution that spread all over the whole zone from particulate to large particle diameter. Therefore, adopt the high crystallization silver powder that the present invention relates to, make silver paste, the electrically conductive film that adopts this silver paste to form, heat-resisting shrinkage is good, and the surface roughness of electrically conductive film is smooth. Therefore, adopt conductive paste, the raising of the conductor quality that can seek to form.
In addition, the manufacture method of high crystallization silver powder of the present invention is for adding the solution that contains reducing agent and water-soluble organic acid, the method that its reduction is separated out in the solution that contains silver salt. By the existence of this water-soluble organic acid, the high crystallization silver powder that can easily make high crystallization and have sharp-pointed size distribution is suitable for the industrial production operation.
Claims (12)
1. the manufacture method of a high crystallization silver powder, it adopts arabo-ascorbic acid and/or ascorbic acid as reducing agent, makes silver powder from the solution that contains silver ion, it is characterized in that,
Preparation is with gelatin, silver nitrate and nitric acid the 1st aqueous solution soluble in water, and the 2nd aqueous solution that has dissolved water-soluble organic acid and arabo-ascorbic acid and/or ascorbic acid,
Then, slowly add the 2nd aqueous solution in the 1st aqueous solution, interpolation is stirred after stopping, and makes the particle growth and generates silver particles, then, leaves standstill and makes the silver particles sedimentation, and discarded supernatant filters, washs, and obtains high crystallization silver powder.
2. according to the manufacture method of the described high crystallization silver powder of claim 1, wherein, the concentration of the gelatin in above-mentioned the 1st aqueous solution is 2g/L～10g/L.
3. according to the manufacture method of claim 1 or 2 described high crystallization silver powder, wherein, the concentration of the silver nitrate in above-mentioned the 1st aqueous solution is 50g/L～150g/L with the silver metering.
4. according to the manufacture method of any one described high crystallization silver powder in the claim 1～3, wherein, add aqueous solution of nitric acid and make the concentration adjustment of the free nitric acid in above-mentioned the 1st aqueous solution become 40g/L～120g/L.
5. according to the manufacture method of any one described high crystallization silver powder in the claim 1～4, wherein, the arabo-ascorbic acid in above-mentioned the 2nd aqueous solution and/or the concentration of ascorbic acid are 45g/L～120g/L.
6. according to the manufacture method of any one described high crystallization silver powder in the claim 1～5, wherein, the concentration of the water-soluble organic acid in above-mentioned the 2nd aqueous solution is 1g/L～50g/L.
7. according to the manufacture method of the described high crystallization silver powder of claim 6, wherein, above-mentioned water-soluble organic acid is any or composition more than 2 kinds of DL-malic acid, citric acid, formic acid, valeric acid, isovaleric acid, butanedioic acid, propionic acid, lactic acid, adipic acid.
8. a silver powder is characterized in that, adopts the manufacture method of any one described high crystallization silver powder in the claim 1～7 to obtain.
9. according to the described high crystallization silver powder of claim 8, it is characterized in that primary particle size is that 0.07 μ m～4.5 μ m, crystallite particle diameter are more than 200 .
10. according to the described high crystallization silver powder of claim 8, it is characterized in that the volume cumulative mean particle diameter D that adopts laser diffraction and scattering formula particle size distribution method to measure
50Be 0.1 μ m～5.0 μ m, size distribution index (D
90-D
10)/D
50Value be below 1.5.
11., it is characterized in that the volume accumulation maximum particle diameter D that adopts laser diffraction and scattering formula particle size distribution method to measure according to the described high crystallization silver powder of claim 8
MaxBe below the 16.0 μ m.
12., it is characterized in that its specific area is 0.2m according to the described high crystallization silver powder of claim 8
2More than/the g.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP196627/2005 | 2005-07-05 | ||
| JP2005196627A JP5032005B2 (en) | 2005-07-05 | 2005-07-05 | High crystal silver powder and method for producing the high crystal silver powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101218051A true CN101218051A (en) | 2008-07-09 |
Family
ID=37604510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800245267A Pending CN101218051A (en) | 2005-07-05 | 2006-07-04 | Highly crystalline silver powder and process for production of the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20090116998A1 (en) |
| EP (1) | EP1930104A1 (en) |
| JP (1) | JP5032005B2 (en) |
| KR (1) | KR20080022580A (en) |
| CN (1) | CN101218051A (en) |
| TW (1) | TW200719992A (en) |
| WO (1) | WO2007004649A1 (en) |
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-
2005
- 2005-07-05 JP JP2005196627A patent/JP5032005B2/en active Active
-
2006
- 2006-07-04 WO PCT/JP2006/313320 patent/WO2007004649A1/en active Application Filing
- 2006-07-04 KR KR1020087001323A patent/KR20080022580A/en not_active Application Discontinuation
- 2006-07-04 US US11/994,921 patent/US20090116998A1/en not_active Abandoned
- 2006-07-04 EP EP06767837A patent/EP1930104A1/en not_active Withdrawn
- 2006-07-04 CN CNA2006800245267A patent/CN101218051A/en active Pending
- 2006-07-05 TW TW095124458A patent/TW200719992A/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TW200719992A (en) | 2007-06-01 |
| US20090116998A1 (en) | 2009-05-07 |
| JP5032005B2 (en) | 2012-09-26 |
| TWI315229B (en) | 2009-10-01 |
| WO2007004649A1 (en) | 2007-01-11 |
| KR20080022580A (en) | 2008-03-11 |
| JP2007016258A (en) | 2007-01-25 |
| EP1930104A1 (en) | 2008-06-11 |
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